Saturated indane derivatives and processes for producing same

ABSTRACT

Saturated indane derivatives having the formula WHEREIN R is a carbonyl oxygen, a hydroxy group, an acyloxy group, or an alkyloxy group; perfume compositions containing such indane derivatives; and process for producing same.

Unite States Patent Theimer [451 Aug. 1, 1972.

[54] SATURATED INDANE DERIVATIVES AND PROCESSES FOR PRODUCING SAME [72]Inventor: Ernst T. Theimer, Rumson, N1.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

[22] Filed: Aug. 18, 1969 [21] App1.No.: 851,048

[5 6] References Cited OTHER PUBLICATIONS Moller, Chemistry of OrganicCompounds 3rd Edition, pp. 150- 152, (1965) Appel et a1. J. Chem. Soc.Vol. 1959 pp. 3322 Moun, Chem. Abstracts" Vol. 57 pp. 7317- 7319, (1962)Dutta et al., Chem. Abstracts Vol. 59, p. 468C, (1963) Primary Examinerl,eon Zitver Assistant Examiner-Norman Morgenstern Attorney-Ward,McElhannon, Brooks & Fitzpatrick [57] ABSTRACT Saturated indanederivatives having the formula &

wherein R is a carbonyl oxygen, a hydroxy group, an acyloxy group, or analkyloxy group; perfume compositions containing such indane derivatives;and process for producing same.

3 Claims, No Drawings SATURATED INDANE DERIVATIVES AND PROCESSES FORPRODUCING SAME BACKGROUND OF THE INVENTION There is a continuing needfor fragrance materials having desirable woody amber odors withsatisfactory olfactory overtones or qualities. Many natural productshave such woody amber fragrances, but the more desirable of these arefrequently in short supply, and

hence difficult to obtain and expensive. Further, while both natural andsome synthetic materials can provide woody amber fragrance qualities,many of these are fleeting and unsuitable for use in quality perfumes orother olfactory compositions. Moreover, it is desirable to have suchfragrance materials with musk, fruit-like, or similar overtones whichcan be blended with other materials.

THE INVENTION Briefly, the present invention provides novel saturatedindane derivatives having the formula having the formula The indanolsand derivatives contemplated according to this disclosure includel,l,2,3,3-pentamethylhexahydroindan-4-ol having the formula l l,2,3,3-pentamethylhexahydroindan-S-ol having the formula thecorresponding indanyl alkyl ethers according to the formulas j@ o m andthe corresponding indanyl esters according to the and formulas ;/\O OR2and ln the foregoing formulas R is a lower alkyl group,

desirably one having from one to five carbon atoms, with methyl being apreferred lower alkyl group; and R is a lower alkyl acyl group havingfrom one to five carbon atoms, with the acetyl group being preferred. Itwill be appreciated from the present disclosure that the foregoingmaterials can exist in several stereoisomeric forms, and it iscontemplated that the formulas given above include the several isomericforms.

The alcohols can be prepared directly from the correspondingpentamethylindane by sulfonation, alkali fusion, and hydrolysis toprovide pentamethylindanol and then hydrogenation to thehexahydropentamethylindanol. Alternatively, the saturated3a,7aepoxypentamethylindane can be treated with an aluminum trialkoxideto form the monounsaturated alcoho].

The alcohols can also be produced directly from pentamethylindane bytreatment with an acyl halide such as acetyl chloride or the like in thepresence of a Friedel-Crafts catalyst followed by oxidation of theindane-alkyl ketone with a peroxygen material such as peracetic acid andthe like to provide the indanyl ester. Hydrolysis of the ester providesthe indanol which is then hydrogenated as set forth below to afford thesaturated indanol. A tetrahydroindanol can also be obtained by Birchreduction of S-indanol as shown in J. Am. Chem. Soc., 89, 1044. Thetetrahydroindanols so prepared are then hydrogenated and oxidized to theketone, as taught hereinafter.

The ketones of this invention can be produced by a number of routes. Onepreferred route is the oxidation of a saturated or unsaturated 4-indanolor S-indanol under conditions providing the corresponding ketone.According to this preferred route, any reagent which will convert asecondary hydroxyl to a carbonyl oxygen can be used. Exemplary of suchoxidizing agents are Jones reagent (a chromium trioxide-sulfuric acidmixture) and oxygen-metal systems.

The oxidation of the hydroxyl group is carried out on a hydrogenatedindanol. In the event that the ketone is not saturated the six-memberedring is subsequently hydrogenated with a catalyst under conditions whichwill not reduce the carbonyl group. Suitable catalysts for this reactioninclude metallic catalysts such as Raney nickel, or noble metals such asplatinum, palladium, and the like utilized at substantiallysuperatmospheric pressures on the order of 50 to 125 atmospheres. it ispreferred to carry out the hydrogenation at from 1,000 to about 1,500psig at l50 to 250 C.

The oxidation is carried out by treating the secondary alcohol withhexavalent chromium or oxygen-metallic catalyst oxidizing systems. It isdesirable in carrying out such a reaction that the alcohol be dissolvedor dispersed in a reaction vehicle which serves to moderate the reactionand provide better control. Suitable vehicles include oxygenatedsolvents such as acetone or lower carboxylic acids such as acetic acid.It will be understood that mutual solubility of the indanyl alcohol andoxidizing agent in the reaction vehicle is preferred.

The Jones reagent is prepared by dissolving chromium trioxide or alkalimetal dichromate in aqueous sulfuric acid, e.g., 30 to 50 percent H S)Opreferably 40 percent H2804. At least an equimolar quantity of theoxidizing agent is mixed with the indanol in, the reaction vehicle forbest results. it is preferred to use an excess of oxidizing agent up toabout 50 molar percent based upon the weight of the indanol, and a molarexcess of 25 to 40 percent is preferred The oxidation is carried out atmild temperatures on the order of l30 C. In a preferred embodiment ofthe invention, the reaction is carried out at l520 C.

The oxidation to provide the ketones can also be carried out with theoxygen-metallic catalyst system disclosed above. In this case the oxygencaneither be pure or in admixture with an inert diluent such as nitrogenor the like. The catalyst is preferably a metal such as silver. Coppercan also be used.

After the reaction to produce the ketone is completed, the product canbe separated from the vehicle and any unreacted materials or unwantedbyproducts removed by conventional means including washing,distillation, crystallization, extraction, preparative chromatography,and the like. it is preferred to fractionally distill the washedreaction product under relatively high vacuum so as to obtain a pureproduct. Product purities of 80 percent are readily obtained, and muchhigher purities can also be provided by suitable treatment. All parts,proportions, percentages and ratios herein are by weight unlessotherwise indicated.

The pentamethylhexahydroindanones of this invention are useful asfragrances. They can be used singly or in combination to contribute awoody amber fragrance.

As olfactory agents the indanones of this invention can be formulatedinto or used as components of a perfume composition.

The term perfume composition is used herein to mean a mixture of organiccompounds, including, for example, alcohols, aldehydes, ketones, estersand frequently hydrocarbons which are admixed so that the combined odorsof the individual components produce a pleasant or desired fragrance.Such perfume compositions usually contain: (a) the main note or thebouquet or foundation-stone of the composition; (b) modifiers whichround off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation, and substances which retardevaporation; and (d) top-notes which are usually lowboilingfresh-smelling materials.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereofcan be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of the compounds of this invention which will be eflective inperfume compositions depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 2 percentby weight of mixtures or compounds of this invention, or even less, maybe used to impart a woody amber odor to soaps, cosmetics, and otherproducts. The amount employed can range up to 7 percent or higher andwill depend on considerations of cost, nature of the end product, theeffect desired on the finished product and the particular fragrancesought.

The indanones of this invention can be used alone or in a perfumecomposition as olfactory components in detergents and soaps; spacedeodorants; perfumes; colognes; bath preparations such as bath oil andbath salts; hair preparations such as lacquers, brilliantines, pomadesand shampoos; cosmetic preparations such as creams, deodorants, handlotions and sun screens; powders such as talcs, dusting powders, facepowder, and the like. When used as an olfactory component of a perfumedarticle, as little as 0.01 percent of the novel ketones will suffice toimpart a woody amber odor.

In addition, the perfume composition can contain a vehicle or carrierfor the other ingredients. The vehicle can be a liquid such as alcohol,glycol, or the like. The carrier can be an absorbent solid such as a gumor components for encapsulating the composition.

It will also be appreciated that the pentamethylhexahydroindanonesaccording to this invention can be used to enhance, modify, orsupplement the fragrance properties of natural or synthetic fragrancecompositions. Thus, the indanones can be used in fragrance compositionsfor addition to perfume compositions or directly to products such assoap, detergents, cosmetics, and the like. The fragrance compositions soprepared do not entirely provide the olfactory properties to thefinished perfume or other article, but they do EXAMPLE I a. Preparationof Pentarnethylindanesulfonic Acid A 5-liter flask equipped with astirrer, condenser, and dropping funnel is charged with 1,500 g ofconcentrated sulfuric acid, and 400 g of l,l,2,3,3-pentamethylindane isadded dropwise while the temperature is maintained at 3035 C. Afteraddition is completed stirring is continued for an additional hour.

A 5-liter flask is se up with a thermometer and stirrer and immersed ina dry ice-isopropanol bath, and 1 liter of water is charged to theflask. After the water is cooled to C the foregoing reaction mixture isadded dropwise to the water while the 10 temperature is maintained. Theaddition of reaction mixture to the water is completed and the stirringis continued for 30 minutes before filtering the flask contents througha Buchner funnel under vacuum. The solids so obtained are pressed toremove water.

The solids are rinsed in 100 ml of 1 percent hydrochloric acid at 0 Cand pressed to obtain 822.2 g of crude crystals. After overnight dryingin a vacuum desiccator, the 773.9 g of crude solids are placed in 3liters ofbenzene and refluxed to remove further water. The benzenemixture is cooled to 40 C and filtered, and the benzene is distilled offunder 50 mm Hg to recover l,1,2,3 ,3-pentamethylindanesulfonic acid.

b. Preparation of Pentamethylindanol One mole of the indanesulfonic acidso produced is thoroughly admixed with 2 moles of sodium hydroxide, andthe mixture is heated to the fusion temperature of 360 C and maintainedat that temperature for 2 hours. During the fusion the reaction mass ismechanically agitated.

After the heating is completed, the reaction mass is cooled andextracted with water. The product is then neutralized with dilutehydrochloric acid, and the indanol so produced is extracted withbenzene. The benzene is stripped to provide 1, l,2,3,3-pentamethylindanol.

c. Production of Pentamethylhexahydroindanol Into a 200 ml stainlesssteel autoclave are introduced 70 g of 1,l,2,3,3-pentamethylindan-5-ol,5 g of 5 percent rhodium on carbon catalyst, and 150 ml of isopropylalcohol. While maintaining the temperature within the autoclave at C,hydrogen gas is fed in until a pressure of 1,025 psi is reached. Whilethe hydrogen pressure is maintained at about 1,025 psi, the temperatureof the reaction mass is raised over a period of 3 hours to 178 C (atwhich point the pressure rises to 1,500 psi).

After 18 hours of hydrogenation at 1,500 psi and 178 C, the crudereaction mass is stripped free of solvent. Infrared and NMR analysisindicate that the reaction mass contains l,l,2,3,3-pentamethylindan-5-olhaving the structure Similar reactions are run with a Raney nickelcatalyst at 1,500 psig and 200 C and with a palladium on carbon catalystat 150 psig and 200 C to provide substantially identical results.

A substantially identical reaction is carried out withl,l,2,3,3-pentamethylindan-4-ol to produce l,l,2,3,3-hexahydroindan-4-ol having the formula A 500 ml reaction flask ischarged with 50 g of crude hexahydropentamethylindan-S-ol obtained byhydrogenating the indan-S-ol produced in Example 1. Jones reagent isproduced by dissolving chromium trioxide in 20percent aqueous sulfuricacid. The flask contents are maintained at l5-20 C while ml (0.33 mole)of the Jones reagent is added. The reaction flask contents are thenstirred for one-half hour beyond the thirty minutes required foraddition of the Jones reagent.

The ketone is recovered by adding 25 cc of methanol and 50 cc oftoluene. The organic layer is separated, and the remaining aqueous layeris extracted with toluene. The toluene extract is added to the originalextract, and the organic material is washed to neutrality with water andthen stripped and distilled.

The 33 g of distilled material is admixed with 2 g of Primol mineral oiland antioxidant and distilled at a vapor temperature of 96-l20 C at l-2mm Hg to obtain 23.5 g of the pentamethylhexahydro-S-indanone.

The purified material is a clear liquid boiling at 9699 C at 2.0 mm Hg.The IR spectrum shows significant peaks as follows: at 5.8 microns, at7.1 microns, and at 7.2 and 7.3 microns. These peaks are attributable toa cyclohexanyl ketone, a methylene adjacent to a carbonyl, and togem-dimethyl and methyl respectively. Raman spectrometry does not showthe presence of any carbon-to-carbon unsaturation.

The ketone so obtained has an unmistakeable woody amber odor with a muskquality. This material is compared with a ketone called Ketone BD9, a3,5,5,7,7-pentamethyldecahydro-2-naphthalenone, and it is found that theindanone is a product having a much better woody amber character,whereas said napthalenone has a simple woody aroma. The fragrancecharacteristics are considered to be quite different.

The process set forth in Example II can be carried out with thecorresponding pentamethylhexahydroim dan-4-ol to obtain a fragranceproduct similar to that obtained in Example II.

EXAMPLE III Preparation of 1,1 ,2,3,3-Pentamethylhexahydroindan- 4-olThe following ingredients are charged into a stainless steel five-literautoclave equipped with a hydrogen gas feed:

1,800 g (8.14 moles) of l, 1 ,2,3,3-pentamethylindane (85 percent pure)90 g of Raney nickel.

Enough hydrogen is fed into the autoclave to raise the pressure to 1,000psig. The hydrogen feed is then continued at 3 ml/min, and the autoclaveis heated up to a temperature in the range of l50-185 C over a period of8 hours. During this time the pressure in the autoclave is maintained at1,500 psig.

The 1,641 g of crude product removed from the autoclave is distilled ona 12-inch Goodloe column after being mixed with 10.0 g of Primol mineraloil. The distillate is recovered in two fractions:

Fraction 1: Distills at a temperature of 788 2 C and 4.0 mm Hg toprovide 401 g of 4,5,6,7-tetrahydrol,1,2,3 ,3-pentamethylindane.

Fraction II: Distills at a temperature of 868 8 C and 3.53.8 mm Hg toprovide 729 g of hexahydrol, l ,2,3 ,3-pentamethylindane.

A sample of Fraction 1 is further refined on a 6-foot by inch gas liquidchromatographic (GLC) column containing 20 percent Carbowax polyethyleneglycol and operated at 1 10 C. Analysis by infrared (IR) and protonmagnetic resonance (PMR) confirms the structure:

Into a 250 ml flask equipped with thermometer, stirrer, reflux condenserand ice bath are introduced 195 g of the 'tetrahydroindane producedabove and g of sodium acetate. At 25t0 30C 124g of 40percent peraceticacid (0.65 mole) is added during 4 hours. After addition is completed anequal volume of water is added to the reaction mass. The aqueous phaseis separated from the organic phase and extracted with 150 ml oftoluene. The toluene extract is combined with the organic phase andwashed with 1 volume of Spercent aqueous sodium hydroxide solution andthen with 1 volume of water.

The solvent is stripped off leaving a crude produce weighing 208 g. Thecrude epoxy product is distilled on a 12-inch Goodloe column afteraddition of 4.0 g of triethanolamine at 7274 C and 1.0-1 .4 mm Hg.

Into a 500 ml flask equipped with reflux condenser, stirrer thermometerand addition funnel are introduced 250 cc toluene and 80 g aluminumtriisopropoxide. The mixture is heated to reflux and 90 g of theepoxyhexahydroidane as produced above is added drop-wise over 1 A hoursat reflux. The reaction mass is further refluxed for 10 hours whereuponit is cooled at 25 C.

The cooled reaction mass is poured into a mixture of 500 g ice and 200cc of ISpercent sulfuric acid, stirred for 15 minutes, and separatedinto an aqueous phase and an organic phase. The aqueous phase isextracted with 200 cc toluene, and the toluene extract is combined withthe organic layer. The bulked material is washed with saturated aqueoussodium bicarbonate and twice with 100 cc of water. The solvent isstripped from the washed organic phase to provide a crude productweighing 71 g.

The crude product is distilled on a 4-inch micro- Vigreux column at avapor temperature of l05l07 C and 2.1-2.3 mm Hg to obtain4,5,6,7-tetrahydro- 1,l,2,3, 3-pentamethyl-4-indanol.

Into a 200 mi stainless steel autoclave are introduced 60 g of thetetrahydropentamethyl-4-indanol so produced, 5g of Spercent rhodium oncarbon catalyst, and 150 ml of isopropanol. The temperature of theautoclave is maintained at 20 C while hydrogen gas is fed in to obtain apressure of 1,025 psig. The temperature is then raised to 180 Cwhereupon the temperature rises to 1,500 psig.

After 18 hours of hydrogenation under these conditions, the hydrogen isvented and the autoclave is clave is cooled to room temperature. Thesolvent is stripped ofi to yield a crude product weighing 35 g. Theproduct is washed and distilled to obtain 1 l,2,3,3-pentamethylhexahydroindan-4-ol.

EXAMPLE IV Preparation of 1 ,1 ,2,3 ,3-Pentamethylhexahydro 4( 5H)-indanone Into a 500 ml flask fitted with cooling means, stirrer,thermometer and reflux condenser are introduced 50 g of thehexahydroindan-4-ol produced in Example 111 and 300 ml of acetone. Themixture is stirred while ml of Jones reagent is added. The reactionmixture is then stirred for 1 hour, after which 25 ml of ethanol and 50ml of toluene are added. The aqueous phase is removed and the organicphase is washed and neutralized with sodium bicarbonate.

The solvent is stripped ofi and the remaining organic material isdistilled to provide l,l,2,3,3-pentamethylhexahydro-4-(5l-l)-indanonehaving a woody amber odor with a fruit-like musk quality.

EXAMPLE V Preparation of Soap Compositions A total of g of soap chips ismixed with 1 g of the perfume composition given below until asubstantially homogeneous composition is obtained. The soap compositionmanifests a characteristic woody amber, musklike odor.

The perfume composition consists of the following ingredients:

ingredient Parts Vetivert Oil 40 Ketone Produced in Example 11 60Sandalwood Oil 100 Rose Geranium Oil 200 Musk Extract (3%) 25 CivetExtract (3%) 25 Benyl-iso-Eugenol 100 Coumarin 100 Heliotropin 50 Boisde Rose Oil 200 Benzoin Resin 100 1.000

Similar results are obtained when the ketone of Example 1V is used toreplace the ketone of Example 11.

EXAMPLE VI Preparation of a Detergent Composition A total of 100 g of adetergent powder is mixed with 0.15 g of the perfume composition setforth in Example V until a substantially homogeneous composition havinga woody amber or amber-musk like odor is obtained.

EXAMPLE VII Preparation of a Cosmetic Powder Composition A cosmeticpowder is prepared by mixing 100 g of talcum powder with 0.25 g of theketone obtained from the process of Example II in a ball mill. A secondcosmetic powder is similarly prepared except that the ketone prepared byExample II is replaced by the compound prepared by Example IV. All havewoody amber, musk-like odors.

EXAMPLE VIIl compound to P87 liquid detergent produced by Ultra ChemicalCo.

What is claimed is:

1. Saturated indane derivatives having the formula &

wherein R is a carbonyl oxygen.

2. 1,1,2,3,3-Pentamethylhexahydro-4(5l-l)-indanone.

3. l, l ,2,3,3-Pentamethy1hexahydro-5(4H)-indanone.

2. 1,1,2,3,3-Pentamethylhexahydro-4(5H)-indanone. 3.1,1,2,3,3-Pentamethylhexahydro-5(4H)-indanone.